US4633024A - Process for producing aromatic hydroxy compound - Google Patents

Process for producing aromatic hydroxy compound Download PDF

Info

Publication number
US4633024A
US4633024A US06/728,453 US72845385A US4633024A US 4633024 A US4633024 A US 4633024A US 72845385 A US72845385 A US 72845385A US 4633024 A US4633024 A US 4633024A
Authority
US
United States
Prior art keywords
reaction
mixture
alkali metal
sulfonic acid
aromatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/728,453
Other languages
English (en)
Inventor
Ryuzo Ueno
Kazuyuki Sakota
Yoshiyuki Naito
Mitsuyuki Kishimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ueno Seiyaku Oyo Kenkyujo KK
Original Assignee
Ueno Seiyaku Oyo Kenkyujo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=13338283&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US4633024(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ueno Seiyaku Oyo Kenkyujo KK filed Critical Ueno Seiyaku Oyo Kenkyujo KK
Application granted granted Critical
Publication of US4633024A publication Critical patent/US4633024A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of SO3H groups or a derivative thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof

Definitions

  • This invention relates to an improvement in a process for producing an aromatic hydroxy compound.
  • a process which first went into commercial operation comprises alkali fusion of aromatic sulfonic acid salts. Since this process is suitable for production in a small-scale apparatus, it is still utilized for the production of those aromatic hydroxy compounds whose demand is not so large.
  • the alkali fusion is a reaction of a solid involving phase change from a liquid--a mud--a highly viscous mass--a powder, and during the reaction, stirring of the reaction mixture is extremely difficult.
  • the present inventors have long been engaged in a study of adapting solid-phase reactions to liquid-phase reactions, and made good achievements in the adaptation of the Kolbe-Schmitt reaction to a reaction in suspension. Further investigations into improvement of the alkali fusion of aromatic sulfonic acid salts have led to the present invention.
  • a process for producing an aromatic hydroxy compound which comprises reacting an alkali metal salt of an aromatic sulfonic acid with an alkali metal hydroxide in a reaction medium which is an aliphatic, alicyclic or aromatic hydrocarbon, or an aromatic ether, or a mixture of these.
  • alkali metal salt of aromatic sulfonic acid used in this invention examples include alkali metal salts, such as sodium or potassium salts, of compounds having an aromatic ring, such as benzene, naphthalene, anthracene, phenanthrene, diphenyl, triphenyl, diphenylalkanes, triphenylalkanes, aromatic ring-like compounds fused with hetero rings such as a quinoline ring, and partially hydrogenated products of the foregoing compounds, having one or a plurality of sulfonic acid groups on the aromatic ring.
  • These alkali metal salts of aromatic sulfonic acids may have one or a plurality of substituents which do not affect the reaction, such as an alkyl group, an amino group or a carboxyl group, on the ring or linking chains.
  • alkali metal salts of aromatic sulfonic acids can be obtained in a customary manner by sulfonating the above-exemplified compounds having an aromatic ring with sulfuric acid or fuming sulfuric acid, and converting the sulfonated compounds to alkali metal salts.
  • Sodium hydroxide and potassium hydroxide are preferred as the alkali metal hydroxide.
  • 2 to 10 moles, preferably 2 to 7 moles, of the alkali metal hydroxide is used per sulfonic acid group.
  • Suitable reaction media are aliphatic, alicyclic or aromatic hydrocarbons or aromatic ethers, include light oil, kerosene, lubricant oils, white oil (liquid paraffin), alkylbenzenes, diaryls, complete or partial hydrogenation products of diaryls, diarylalkanes, complete or partial hydrogenation products of diarylalkanes, triaryls, complete or partial hydrogenation products of triaryls, triarylalkanes, complete or partial hydrogenation products of triarylalkanes, diphenyl ether, ditolyl ether, and mixtures of two of the foregoing compounds with each other. They have a boiling point in the range of 200° to 500° C., particularly 250° to 450° C.
  • the alkali metal salt of aromatic sulfonic acid and the alkali metal hydroxide are dispersed in the reaction medium and reacted.
  • the amount of the reaction medium used is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, per part by weight of the alkali metal salt of an aromatic sulfonic acid.
  • the reaction temperature is 200° to 500° C., preferably 250 to 450 C.
  • the reaction time or the residence time is about 0.1 to about 10 hours.
  • the reaction is carried out in an atmosphere of an inert gas such as nitrogen. It may be carried out either under atmospheric pressure or elevated pressures.
  • the reaction mixture can be dehydrated and reacted in a dispersed state. Hence, it can be easily dehydrated, and a uniform reaction mixture can be obtained. Consequently, the following marked improvements can be achieved by the present invention.
  • the dehydration and reaction can be carried out continuously. Since the process can be operated while the reaction mixture is in a uniformly dispersed state, accurate temperature control and transportation become easy. Furthermore, mass production is easy because the process can be carried out completely continuously.
  • reaction mixture can be easily stirred, the apparatus can be simplified, and the power required for stirring can be markedly reduced.
  • reaction mixture can be easily maintained flowable, it is not necessary to perform the reaction under high pressures in the presence of a large amount of water.
  • the process of this invention is industrially excellent since it can provide large quantities of the desired products of high quality at low costs.
  • the process of this invention can be carried out either batchwise or continuously.
  • the accompanying drawing is a diagram showing an embodiment of this invention by a continuous method.
  • the alkali fusion reaction and the work-up can be carried out as follows:
  • An aqueous solution of an alkali metal hydroxide (A) and an aromatic sulfonic acid alkali metal salt (B) are mixed with stirring in a mixing tank 1, and in a dispersing tank 2, a reaction medium C is added to disperse A and B.
  • the dispersion is dehydrated in a dehydrating tank 3, and then a dispersed mixture composed of the alkali metal salt of aromatic sulfonic acid, the alkali metal hydroxide and the reaction medium is stored in a reservoir 4.
  • reaction medium C instead of the aqueous solution of alkali metal hydroxide (A) to the mixing tank 1, and to feed the aqueous solution of alkali metal hydroxide (A) instead of the reaction medium C to the dispersing tank 2 in the above procedure.
  • the mixture is sent to a reaction tank 5 where it is reacted with stirring at the reaction temperature and with the residence time described hereinabove.
  • the above operation is preferably carried out in an atmosphere of nitrogen.
  • the reaction mixture from the reaction tank 5 is preferably cooled by a heat exchanger 6, and then mixed with water D with stirring in a water-mixing tank 7. Subsequently, the mixture is separated into a reaction medium layer and an aqueous layer in a separating tank 8.
  • the reaction medium E is recovered from the separating tank 8.
  • the aqueous layer is transferred from the separating layer 8 to a decolorization tank 9 to decolorize it with a decolorizer F.
  • the decolorizer is separated by a filtration device 10, and the filtrate is sent to an acid precipitation tank 11.
  • An acid G is added to precipitate the filtrate.
  • the desired product H is obtained by separation in a separating device such as a centrifugal separator 12.
  • Biphenyl (154 g) was melted in a reaction vessel, and while it was maintained at 155° to 160° C., 392 g of concentrated sulfuric acid was added dropwise. They were reacted at this temperature for 1.5 hours. After cooling, the reaction mixture was dissolved in 2 liters of water, and an aqueous solution of potassium hydroxide was added to give 375 g of dipotassium 4,4'-biphenyldisulfonate.
  • Dipotassium 4,4'-biphenyldisulfonate (195 g) was added to 448 g of a 50% aqueous solution of potassium hydroxide, and the mixture was stirred. Then, 1680 g of a hydrogenated triphenyl mixture was mixed. The mixture was heated to 310° C. in an atmosphere of nitrogen, and with stirring, it was dehydrated. Thereafter, the mixture was stirred at 310° C. for 3 hours. After cooling, 1 liter of water was added to the reaction mixture to separate the triphenyl hydrogenated layer. The water layer was decolorized with activated carbon, and precipitated with dilute sulfuric acid to give 88.9 g (yield 95.6%) of 4,4'-biphenol.
  • Sodium naphthalene-2-sulfonate (230 g) was suspended in 795 g of dibenzyltoluene, and 176 g of a 50% aqueous solution of sodium hydroxide was added. The mixture was stirred under a nitrogen stream and heated to 300° C. to dehydrate it. The dehydrated mixture was stirred at 310° C. for 3 hours. After cooling, 1.2 liters of water was added to the reaction mixture to separate the reaction medium layer. The aqueous layer was decolorized with activated carbon and then precipitated with an acid to give 133.2 g (yield 92.5%) of 2-naphthol.
  • Disodium m-benzenedisulfonate (282 g), 328 g of a 50% aqueous solution of sodium hydroxide and 860 g of white oil were mixed, and heated to 300° C. in a nitrogen stream to dehydrate the mixture. The dehydrated mixture was stirred at 320° C. for 1 hour. After cooling, 400ml of water was added to the reaction mixture to separate the reaction medium layer. The aqueous layer was acidified, and the precipitated bisulfite was separated by filtration. The filtrate was extracted with 100 ml of butyl acetate, and the solvent was evaporated to give 103.8 g (yield 94.4%) of resorcinol.
  • a 50% aqueous solution of potassium hydroxide and dipotassium 4,4'-biphenyldisulfonate were sent to a mixing tank 1 at a rate of 896 kg/hr and 390 kg/hr, respectively, and mixed with stirring.
  • a hydrogenated triphenyl mixture was added to the resulting mixture in a dispersing tank 2 at a rate of 2900 kg/hr to disperse them.
  • the dispersed mixture was dehydrated in a dehydrating tank 3, and then sent to a reservoir.
  • the dehydrated mixture of dipotassium 4,4'-biphenyldisulfonate, potassium hydroxide and hydrogenated triphenyl mixture was sent to a reaction tank 5 at a rate of 4190 kg/hr, and continuously reacted at 310° C. with a residence time of 6 hours in a nitrogen stream.
  • the mixture was cooled by a heat exchanger 6, and sent to a water mixing tank 7 where it was mixed with 2000 liters/hr of water.
  • a separating tank 8 the reaction medium layer was separated, and the aqueous layer was mixed with 45 kg/hr of activated tank in a mixing tank 9.
  • the activated carbon was removed in a filtration device 10, and the residue was precipitated with dilute sulfuric acid in an acid precipitating tank 11.
  • a centrifugal separator 12 By separation in a centrifugal separator 12, 178 kg (yield 95.7%) of 4,4'-biphenyl was obtained hourly.
  • Dipotassium 2,6-naphthalenedisulfonate (364 g) was added to 560 g of a 50% aqueous solution of potassium hydroxide, and the mixture was stirred. Then, 2500 g of a hydrogenated triphenyl mixture was mixed, and the resulting mixture was heated to 310° C. in a nitrogen stream and dehydrated with stirring. The mixture was then stirred at 310° C. for 3 hours. After cooling, 2 liters of water was added to the reaction mixture to separate the hydrogenated triphenyl layer. The aqueous layer was decolorized with activated carbon, and precipitated with dilute sulfuric acid to give 148.2 g (yield 92.6%) of 2,6-dihydroxynaphthalene.
  • Trisodium 5-sulfoisophthalate (312 g) was added to 170 g of a 50% aqueous solution of sodium hydroxide, and the mixture was stirred. Then, 1980 g of 1-phenyl-1-(2,3-dimethylphenyl)-ethane was mixed, and the resulting mixture was heated to 280° C. in a nitrogen stream and dehydrated with stirring. The dehydrated mixture was stirred at 280° C. for 1.5 hours. After cooling, 1 liter of water was added to the reaction mixture to separate the reaction medium. The aqueous layer was decolorized with activated carbon, and precipitated with dilute sulfuric acid to give 172.5 g (yield 94.8%) of 5-hydroxyisophthalic acid.
  • Sodium quinoline-8-sulfonate (231 g) was added to 170 g of a 50% aqueous solution of sodium hydroxide, and the mixture was stirred. Then, 900 g of a hydrogenated triphenyl mixture was mixed, and the mixture was dehydrated. The dehydrated mixture was reacted at 260° C. for 15 minutes in a nitrogen stream. After cooling, 600 ml of water was added to the reaction mixture to separate the reaction medium layer. The aqueous layer was decolorized with activated carbon, acidified and then extracted with 200 ml of chloroform. The chloroform was recovered to give 140.9 g (yield 97.2%) of 8-hydroxyquinoline.
  • Disodium 2-hydroxynaphthalene-3,6-disulfonate (348 g) was added to 176 g of a 50% aqueous solution of sodium hydroxide, and the mixture was stirred. Then, 900 g of a hydrogenated triphenyl mixture was mixed, and the resulting mixture was dehydrated. The dehydrated mixture was reacted at 270° C. for 1.5 hours in a nitrogen stream. After cooling, 2 liters of water was added to the reaction mixture to separate the reaction medium layer. The aqueous layer was decolorized with activated carbon, and then precipitated with an acid to give 231 g (yield 96.3%) of 2,3-dihydroxynaphthalene-6-sulfonic acid.
  • Sodium naphthalene-2-sulfonate and a hydrogenated triphenyl mixture were sent to a mixing tank 1 at a rate of 230 kg/hr and 825 kg/hr, respectively, and mixed with stirring.
  • a dispersing tank 2 200 kg/hr of a 50% aqueous solution of sodium hydroxide was added to form a dispersed mixture.
  • the dispersed mixture was dehydrated in a dehydrating tank 3, and sent to a reservoir 4. From the reservoir 4, a mixture consisting of sodium naphthalene-2-sulfonate, sodium hydroxide and the hydrogenated triphenyl mixture was sent to a reaction tank 5 at a rate of 1155 kg/hr, and continuously reacted at 310° C.
  • the reaction mixture was cooled in a heat exchanger 6, and sent to a water mixing tank 7 where it was mixed with 1200 liters/hr of water. Then, the reaction medium layer was separated in a separating tank 8, and the aqueous layer was mixed with 3.1 kg/hr of activated carbon in a mixing tank 9. Then, the activated carbon was removed in a filtration device 10. The residue was precipitated with dilute sulfuric acid in an acid precipitation tank 11, and separated by a centrifugal separator 12 to give 137.2 g (yield 95.3%) of 2-naphthol hourly.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Quinoline Compounds (AREA)
US06/728,453 1982-04-23 1985-05-01 Process for producing aromatic hydroxy compound Expired - Fee Related US4633024A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP57067209A JPS58185532A (ja) 1982-04-23 1982-04-23 芳香族ヒドロキシ化合物の製法
JP57-67209 1982-04-23

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06487459 Continuation 1983-04-22

Publications (1)

Publication Number Publication Date
US4633024A true US4633024A (en) 1986-12-30

Family

ID=13338283

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/728,453 Expired - Fee Related US4633024A (en) 1982-04-23 1985-05-01 Process for producing aromatic hydroxy compound

Country Status (8)

Country Link
US (1) US4633024A (enrdf_load_stackoverflow)
EP (1) EP0092772B2 (enrdf_load_stackoverflow)
JP (1) JPS58185532A (enrdf_load_stackoverflow)
KR (1) KR870000494B1 (enrdf_load_stackoverflow)
CA (1) CA1235432A (enrdf_load_stackoverflow)
DE (1) DE3364658D1 (enrdf_load_stackoverflow)
ES (1) ES8406409A1 (enrdf_load_stackoverflow)
IL (1) IL68445A0 (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4922031A (en) * 1988-01-23 1990-05-01 Basf Aktiengesellschaft Preparation of 4,4'-dihydroxybiphenyl
US5008472A (en) * 1988-09-17 1991-04-16 Basf Aktiengesellschaft Preparation of 4,4"-dihydroxyterphenyl
US5322946A (en) * 1990-10-04 1994-06-21 Kawasaki Steel Corporation Process for producing aromatic hydroxy compound
CN100497280C (zh) * 2006-01-17 2009-06-10 沈阳化工研究院 一种对苯基苯酚的制备方法
CN102070428A (zh) * 2010-12-18 2011-05-25 宁波尖锋紫星生物科技有限公司 一种合成3-羟基苯乙酮的方法
CN108329195A (zh) * 2018-04-16 2018-07-27 南通柏盛化工有限公司 一种合成2,7-二羟基萘的方法
CN113929561A (zh) * 2020-06-29 2022-01-14 王兴路 一种制备酚类化合物的碱熔方法
CN116375548A (zh) * 2021-12-24 2023-07-04 王兴路 一种制备酚类化合物的连续化碱熔方法及其装置

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0662471B2 (ja) * 1985-09-20 1994-08-17 三井石油化学工業株式会社 ２，６−ジヒドロキシナフタレンの製造方法
IL113142A0 (en) * 1995-03-27 1995-06-29 Icl Israel Chemical Ltd Process for the preparation of 5-hydroxyisophthalic acids
DE19651040C2 (de) * 1996-12-09 1999-01-28 Bayer Ag Verfahren zur Herstellung von 2-Amino-5-alkyl-phenolen
CN104447215B (zh) * 2014-10-29 2016-01-20 绍兴奇彩化工有限公司 一种合成2-萘酚的连续酸化工艺
CN106588575A (zh) * 2016-12-02 2017-04-26 沈阳化工研究院有限公司 一种2,6‑二羟基萘的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2111973A (en) * 1936-01-11 1938-03-22 Antoxygen Inc Hydroxylation of organic compounds
US2334488A (en) * 1941-06-18 1943-11-16 Allied Chem & Dye Corp Manufacture of aromatic hydroxy compounds
US2735873A (en) * 1956-02-21 Process for the preparation of phenol
US2831895A (en) * 1955-12-02 1958-04-22 Dow Chemical Co Phenols from aromatic sulfonic, sulfamic, and sulfone compounds

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE411155C (de) * 1920-12-08 1925-03-24 Chemical T J C Res Company Ltd Verfahren zur Durchfuehrung von chemischen Umsetzungen
DE1493734A1 (de) * 1965-08-12 1969-06-19 Hoechst Ag Vorrichtung zur Herstellung von Alkalisalzen aromatischer Hydroxyverbindungen
JPS6023095B2 (ja) * 1976-02-19 1985-06-05 丸善石油株式会社 アルキルフエノ−ルの製造方法
JPS5343490A (en) * 1976-10-01 1978-04-19 Seiko Instr & Electronics Ltd Tuning fork type crystal vibrator
FR2459215A1 (fr) * 1979-06-15 1981-01-09 Inst Neftekhimicheskikh Prot Procede de preparation de l'a-naphtol
US4243822A (en) * 1979-08-31 1981-01-06 Buffalo Color Corporation Process for the manufacture of 4,4' dihydroxydiphenyl

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2735873A (en) * 1956-02-21 Process for the preparation of phenol
US2111973A (en) * 1936-01-11 1938-03-22 Antoxygen Inc Hydroxylation of organic compounds
US2334488A (en) * 1941-06-18 1943-11-16 Allied Chem & Dye Corp Manufacture of aromatic hydroxy compounds
US2831895A (en) * 1955-12-02 1958-04-22 Dow Chemical Co Phenols from aromatic sulfonic, sulfamic, and sulfone compounds

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4922031A (en) * 1988-01-23 1990-05-01 Basf Aktiengesellschaft Preparation of 4,4'-dihydroxybiphenyl
US5008472A (en) * 1988-09-17 1991-04-16 Basf Aktiengesellschaft Preparation of 4,4"-dihydroxyterphenyl
US5322946A (en) * 1990-10-04 1994-06-21 Kawasaki Steel Corporation Process for producing aromatic hydroxy compound
CN100497280C (zh) * 2006-01-17 2009-06-10 沈阳化工研究院 一种对苯基苯酚的制备方法
CN102070428A (zh) * 2010-12-18 2011-05-25 宁波尖锋紫星生物科技有限公司 一种合成3-羟基苯乙酮的方法
CN102070428B (zh) * 2010-12-18 2013-11-20 宁波尖锋紫星生物科技有限公司 一种合成3-羟基苯乙酮的方法
CN108329195A (zh) * 2018-04-16 2018-07-27 南通柏盛化工有限公司 一种合成2,7-二羟基萘的方法
CN108329195B (zh) * 2018-04-16 2021-05-07 南通柏盛药业有限公司 一种合成2,7-二羟基萘的方法
CN113929561A (zh) * 2020-06-29 2022-01-14 王兴路 一种制备酚类化合物的碱熔方法
CN116375548A (zh) * 2021-12-24 2023-07-04 王兴路 一种制备酚类化合物的连续化碱熔方法及其装置

Also Published As

Publication number Publication date
EP0092772A1 (en) 1983-11-02
ES521743A0 (es) 1984-07-01
DE3364658D1 (en) 1986-08-28
CA1235432A (en) 1988-04-19
JPH0235732B2 (enrdf_load_stackoverflow) 1990-08-13
KR840004708A (ko) 1984-10-24
IL68445A0 (en) 1983-07-31
EP0092772B2 (en) 1993-03-17
ES8406409A1 (es) 1984-07-01
JPS58185532A (ja) 1983-10-29
KR870000494B1 (ko) 1987-03-12
EP0092772B1 (en) 1986-07-23

Similar Documents

Publication Publication Date Title
US4633024A (en) Process for producing aromatic hydroxy compound
US4239913A (en) Process for preparing 2-hydroxynaphthalenecarboxylic acids
US2807643A (en) Preparation of aromatic acids and salts thereof
EP0327221B1 (en) Process for production of aromatic hydroxycarboxylic acid
KR20050062574A (ko) 히드록시벤조산류의 제조방법
EP0834494B1 (en) Process for preparing hydroxybenzoic acids
EP0053824B1 (en) Process for the production of 2-hydroxynaphthalene-6-carboxylic acid
US4780567A (en) Process for producing aromatic hydroxycarboxylic acids
KR870000202B1 (ko) 2-히드록시나프탈렌-6-카르복실산의 선택적 제조방법
CA1182471A (en) Process for preparation of 2-hydroxynaphthalene-3- carboxylic acid
KR950001676B1 (ko) 방향족 히드록시 화합물의 제조방법
JPS622578B2 (enrdf_load_stackoverflow)
US2132357A (en) Carboxylation of alkali metal salts of phenols
US3532745A (en) Method for preparing p-hydroxybenzoic acid
US5643494A (en) Process for the preparation of aromatic hydroxy carboxylic acids
SU401659A1 (ru) Способ выделения 2,5-дихлорфенола
US4072707A (en) Preparation of 3,5-dialkyl-4-hydroxybenzoic acid
US5808142A (en) Process for the preparation of 2-hydroxynaphthalene-6-carboxylic acid
JPS6136A (ja) ２．６−ジ−ｔｅｒｔ−ブチルフエノ−ルの製造方法
US2588336A (en) Purification of gentisic acid
EP0461272B1 (en) Process for producing 4,4'-dihydroxydiphenyl sulfone
JPH04182443A (ja) 芳香族ヒドロキシ化合物の製造方法
CA1263868A (en) Process for producing aromatic hydroxycarboxylic acids
US2822389A (en) Separation of c10 dicarboxylic acids
JPH0551336A (ja) 芳香族ヒドロキシ化合物の製造方法

Legal Events

Date Code Title Description
FEPP Fee payment procedure

Free format text: PAT HLDR NO LONGER CLAIMS SMALL ENT STAT AS INDIV INVENTOR (ORIGINAL EVENT CODE: LSM1); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19981230

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362